Uncontrolled growth of microorganisms in industrial production systems can have serious consequences such as lowered product quality, degradation or spoilage of products, contamination of products, and interference with a wide range of important industrial processes. Growth of microorganisms on surfaces exposed to water (e.g., recirculation systems, heat exchangers, once-through heating and cooling systems, pulp and paper process systems, etc.) can be especially problematic, as many of these systems provide an environment suitable for growth of bacteria and other types of microorganisms. Industrial process waters often provide conditions of temperature, nutrients, pH, etc. that allow for growth of microorganisms in the water and on submerged surfaces. Uncontrolled growth of microorganisms is often manifested in the water column with large numbers of free-floating (planktonic) cells as well as on submerged surfaces where conditions favor formation of biofilms.
Biofilm formation is a serious problem in aqueous industrial systems. Biofilm formation begins when planktonic cells contact submerged surfaces either as a result of turbulence in water flow or by active movement toward the surface. If conditions are favorable for growth, microorganisms can attach to the surface, grow, and begin to produce biopolymers that provide three-dimensional integrity to the biofilm. Over time, the biofilm becomes thicker and internally complex as cells reproduce and produce more biopolymers. The microbial community of a biofilm can consist of single or multiple species.
Many types of processes, systems, and products can be adversely affected by uncontrolled growth of microorganisms in biofilms and in industrial process waters. Such problems include accelerated corrosion of metals, accelerated decomposition of wood and other biodegradable materials, restricted flow through pipes, plugging or fouling of valves and flow-meters, and reduced heat exchange or cooling efficiency on heat exchange surfaces. Biofilms may also be problematic relative to cleanliness and sanitation in medical equipment, breweries, wineries, dairies and other industrial food and beverage process water systems. Moreover, sulfate-reducing bacteria are often problematic in waters used for the secondary recovery of petroleum or for oil drilling in general. Although sulfate-reducing bacteria can form biofilms on equipment and in pipelines, the significant problem caused by these bacteria is that they generate metabolic by-products that have highly offensive odors, are toxic, and can cause corrosion of metal surfaces by accelerating galvanic action. For example, these microorganisms reduce sulfates present in the injection water to generate hydrogen sulfide, a highly toxic gas that has a highly offensive odor (i.e., rotten egg odor), is corrosive, and reacts with metal surfaces to form insoluble iron sulfide corrosion products.
Paper production is particularly susceptible to adverse effects of biofilms. Paper process waters have conditions (e.g., temperature and nutrients) that favor growth of microorganisms in the water and on exposed surfaces. Biofilms in paper process systems are often referred to as slime or slime deposits and contain paper fiber and other materials used in paper production. Slime deposits can become dislodged from system surfaces and become incorporated into the paper, which results in holes and defects or breaks and tears in the sheet. Such problems result in a lower quality product or unacceptable product being rejected. This necessitates stopping paper production to clean the equipment, which results in the loss of production time.
In order to control problems caused by microorganisms in industrial process waters, numerous antimicrobial agents (i.e., biocides) have been employed to eliminate, to inhibit or to reduce microbial growth. Biocides are used alone or in combination to prevent or control the problems caused by growth of microorganisms. Biocides are usually added directly to a process water stream; the typical method of addition is such that the biocide is distributed throughout the process system. In this manner, planktonic microorganisms and those in biofilms on surfaces in contact with the process water can be controlled.
Depending on their chemical composition and mode-of-action, biocides are classified as oxidizing or non-oxidizing. Oxidizing and non-oxidizing biocides can be used alone or in combination, depending on the application. Oxidizing biocides have been widely used in industry for decades, especially in pulp and paper production where strong oxidizers have been used to control microbial populations. Oxidizing biocides such as chlorine gas, sodium hypochlorite, hypobromous acid, and chlorine dioxide are widely used as biocides to treat recirculating waters in many types of industries. Two of the primary reasons for using these and other oxidizing biocides is that such oxidizers are: (1) inexpensive; and (2) non-specific regarding which types of microorganisms are inhibited; if sufficient concentrations of oxidizing biocides are achieved virtually all microorganisms can be inhibited.
Of the oxidizing biocides, chlorine is the most widely used to treat recirculating water systems. The chemistry of chlorine is well known. When added to water, chlorine can exist in either of two forms, HOCl and OCl−, depending on pH. These chemical species of chlorine, also referred to as “free chlorine,” react with a wide variety of organic compounds in aqueous systems.
The highly reactive nature of chlorine may also be a liability, as some of the oxidizer will be used (e.g., consumed) during reactions with non-biological material. Therefore, in order to provide enough oxidizer to react with microorganisms in a process stream, the total amount of oxidizer needed to inhibit microorganisms will include that used in reactions with non-biological components of the system. Reactions with non-biological components of process water not only add to treatment cost, but undesired by-products can be generated and other additives in the process stream can be adversely affected.
Process streams such as in paper mills are especially problematic for highly reactive oxidizers because of the high concentrations of dissolved and particulate inorganic and organic materials. Such process waters exhibit a very high “demand” on the oxidizer. “Demand” is defined as the amount of chlorine that reacts with substances other than the target microorganisms in the process water. In order to maintain an effective concentration of chlorine in an aqueous system to inhibit microorganisms, an amount in excess of the demand must be applied. The types and amounts of inorganic and organic materials in a process stream will define the demand for an oxidizer. For example, many substances are known to react with chlorine and result in the chlorine being non-biocidal; such substances include sulfides, cyanides, metal ions, lignin, and, among others, various water treatment chemicals (e.g., some scale and corrosion inhibitors).
Although effective as biocides, strong oxidizers such as sodium hypochlorite can cause many problems in an industrial process stream such as increased corrosion rates, increased consumption of wet end additives, and, among others, decreased life of felts used on paper machines.
Because of the inherent reactivity of chlorine and related strong oxidizers with non-biological organic and inorganic materials, it is desirable to have the oxidizer in a form that would have antimicrobial activity but be less reactive with non-biological materials. It is known that chlorination of various nitrogen-containing organic and inorganic compounds can reduce the negative effects of chlorine on additives and equipment used in industrial settings. This lower reactivity may also allow the chlorinated nitrogen-species to penetrate a biofilm and react with the microorganisms, rather than be consumed in non-specific reactions with abiotic and inorganic materials in the water.
There remains a need for improved biocides that are effective under harsh environmental conditions such as found in the papermaking industry and other industrial processes.
N-chlorourea, also called monochlorourea (MCU), has been used in many applications, including bleaching (U.S. Pat. No. 3,749,672), delignification from cotton, and textile desizing, and has been used as an herbicide. MCU has also been used as a reaction intermediate in the synthesis of trans-2-chlorocyclopentanol and 2-chlorocyclohexanone. It has been shown that MCU is the initial reaction product in the formation of hydrazine, in which sodium hypochlorite is mixed with urea in the presence of gelatin.